Diferulic acids (also known as dehydrodiferulic acids) are organic compounds that have the general chemical formula C20H18O8, they are formed by dimerisation of ferulic acid. Curcumin and curcuminoids, though having a structure resembling diferulic acids', are not formed that way but through a condensation process. Just as ferulic acid is not the proper IUPAC name, the diferulic acids also tend to have trivial names that are more commonly used than the correct IUPAC name. Diferulic acids are found in plant cell walls, particularly those of grasses.
There are currently nine known structures for diferulic acids. [1] They are usually named after the positions on each molecule that form the bond between them. Included in the group are 8,5'-DiFA (DC) (or decarboxylated form) and 8,8'-DiFA (THF) (or tetrahydrofuran form), which are not true diferulic acids, but probably have a similar biological function. The 8,5'-DiFA (DC) lost CO2 during its formation, the 8,8'-DiFA (THF) gained H2O during its formation. 8,5'-DiFA (BF) is the benzofuran form.
Ferulic acid can also form trimers and tetramers, known as triferulic and tetraferulic acids respectively. [2]
They have been found in the cell walls of most plants, but are present at higher levels in the grasses (Poaceae) and also sugar beet and Chinese water chestnut. [3]
The 8-O-4'-DiFA tends to predominate in grasses, but 5,5'-DiFA predominates in barley bran. [4] [5] Rye bread contains ferulic acid dehydrodimers. [6]
In chufa (tiger nut, Cyperus esculentus) and sugar beet the predominant diferulic acids are 8-O-4'-DiFA and 8,5'-DiFA respectively. [7] [8] 8-5' Non cyclic diferulic acid has been identified to be covalently linked to carbohydrate moieties of the arabinogalactan-protein fraction of gum arabic. [9]
Diferulic acids are thought to have a structural function in plant cell walls, where they form cross-links between polysaccharide chains. They have been extracted attached to a few sugar molecules at both ends, but so far no definitive proof of them linking separate polysaccharide chains has been found. [10] In suspension-cultured maize cells, dimerisation of ferulic acid esterified to polysaccharides occurs mostly in the protoplasm, but may occur in the cell walls when peroxide levels increase due to pathogenesis. [11] In suspension-cultured wheat cells, only the 8,5'-diferulic acid is formed intraprotoplasmically with the other dimers being formed in the cell wall. [12]
Most diferulic acids are not commercially available and must be synthesised in lab. Synthetic routes have been published, but it is often simpler to extract them from plant material. They can be extracted from plant cell walls (often maize bran) by concentrated solutions of alkali, the resulting solution is then acidified and phase separated into an organic solvent. The resulting solution is evaporated to give a mixture of ferulic acid moieties that can be separated by column chromatography. Identification is often by high performance liquid chromatography with a UV detector or by LC-MS. Alternatively they can be derivatised to make them volatile and therefore suitable for GC-MS. Curcumin can be hydrolyzed (alkaline) to yield two molecules of ferulic acid. Peroxidases can produce dimers of ferulic acid, in the presence of hydrogen peroxide through radical polymerization. [13]
Diferulic acids are more effective inhibitors of lipid peroxidation and better scavengers of free radicals than ferulic acid on a molar basis. [14]
The first diferulic acid discovered was the 5,5'-diferulic acid, and for a while this was thought to be the only one. [15]
A carbohydrate is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 and thus with the empirical formula Cm(H2O)n, which does not mean the H has covalent bonds with O. However, not all carbohydrates conform to this precise stoichiometric definition, nor are all chemicals that do conform to this definition automatically classified as carbohydrates.
A hemicellulose is one of a number of heteropolymers, such as arabinoxylans, present along with cellulose in almost all terrestrial plant cell walls. Cellulose is crystalline, strong, and resistant to hydrolysis. Hemicelluloses are branched, shorter in length than cellulose, and also show a propensity to crystallize. They can be hydrolyzed by dilute acid or base as well as a myriad of hemicellulase enzymes.
Polysaccharides, or polycarbohydrates, are the most abundant carbohydrates found in food. They are long-chain polymeric carbohydrates composed of monosaccharide units bound together by glycosidic linkages. This carbohydrate can react with water (hydrolysis) using amylase enzymes as catalyst, which produces constituent sugars. They range in structure from linear to highly branched. Examples include storage polysaccharides such as starch, glycogen and galactogen and structural polysaccharides such as hemicellulose and chitin.
Dietary fiber or roughage is the portion of plant-derived food that cannot be completely broken down by human digestive enzymes. Dietary fibers are diverse in chemical composition and can be grouped generally by their solubility, viscosity and fermentability which affect how fibers are processed in the body. Dietary fiber has two main subtypes: soluble fiber and insoluble fiber which are components of plant-based foods such as legumes, whole grains, cereals, vegetables, fruits, and nuts or seeds. A diet high in regular fiber consumption is generally associated with supporting health and lowering the risk of several diseases. Dietary fiber consists of non-starch polysaccharides and other plant components such as cellulose, resistant starch, resistant dextrins, inulin, lignins, chitins, pectins, beta-glucans, and oligosaccharides.
Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity and do not rot easily. Chemically, lignins are polymers made by cross-linking phenolic precursors.
Bran, also known as miller's bran, is the component of a cereal grain consisting of the hard layers - the combined aleurone and pericarp - surrounding the endosperm. Corn (maize) bran also includes the pedicel. Along with the germ, it is an integral part of whole grains, and is often produced as a byproduct of milling in the production of refined grains. Bran is highly nutritious, but is difficult to digest due to its high fiber content; its high fat content also reduces its shelf life as the oils/fats are prone to becoming rancid. As such, it is typically removed from whole grain during the refining process - e.g. in processing wheat grain into white flour, or refining brown rice into white rice.
Ferulic acid is a hydroxycinnamic acid derivative and a phenolic compound. It is an organic compound with the formula (CH3O)HOC6H3CH=CHCO2H. The name is derived from the genus Ferula, referring to the giant fennel (Ferula communis). Classified as a phenolic phytochemical, ferulic acid is an amber colored solid. Esters of ferulic acid are found in plant cell walls, covalently bonded to hemicellulose such as arabinoxylans. Salts and esters derived from ferulic acid are called ferulates.
Sinapinic acid, or sinapic acid (Sinapine - Origin: L. Sinapi, sinapis, mustard, Gr., cf. F. Sinapine.), is a small naturally occurring hydroxycinnamic acid. It is a member of the phenylpropanoid family. It is a commonly used matrix in MALDI mass spectrometry. It is a useful matrix for a wide variety of peptides and proteins. It serves well as a matrix for MALDI due to its ability to absorb laser radiation and to also donate protons (H+) to the analyte of interest.
The phenylpropanoids are a diverse family of organic compounds that are biosynthesized by plants from the amino acids phenylalanine and tyrosine in the shikimic acid pathway. Their name is derived from the six-carbon, aromatic phenyl group and the three-carbon propene tail of coumaric acid, which is the central intermediate in phenylpropanoid biosynthesis. From 4-coumaroyl-CoA emanates the biosynthesis of myriad natural products including lignols, flavonoids, isoflavonoids, coumarins, aurones, stilbenes, catechin, and phenylpropanoids. The coumaroyl component is produced from cinnamic acid.
Xylan is a type of hemicellulose, a polysaccharide consisting mainly of xylose residues. It is found in plants, in the secondary cell walls of dicots and all cell walls of grasses. Xylan is the third most abundant polysaccharide on Earth, after cellulose and chitin.
Lignocellulose refers to plant dry matter (biomass), so called lignocellulosic biomass. It is the most abundantly available raw material on the Earth for the production of biofuels. It is composed of two kinds of carbohydrate polymers, cellulose and hemicellulose, and an aromatic-rich polymer called lignin. Any biomass rich in cellulose, hemicelluloses, and lignin are commonly referred to as lignocellulosic biomass. Each component has a distinct chemical behavior. Being a composite of three very different components makes the processing of lignocellulose challenging. The evolved resistance to degradation or even separation is referred to as recalcitrance. Overcoming this recalcitrance to produce useful, high value products requires a combination of heat, chemicals, enzymes, and microorganisms. These carbohydrate-containing polymers contain different sugar monomers and they are covalently bound to lignin.
Laccases are multicopper oxidases found in plants, fungi, and bacteria. Laccases oxidize a variety of phenolic substrates, performing one-electron oxidations, leading to cross-linking. For example, laccases play a role in the formation of lignin by promoting the oxidative coupling of monolignols, a family of naturally occurring phenols. Other laccases, such as those produced by the fungus Pleurotus ostreatus, play a role in the degradation of lignin, and can therefore be classed as lignin-modifying enzymes. Other laccases produced by fungi can facilitate the biosynthesis of melanin pigments. Laccases catalyze ring cleavage of aromatic compounds.
The enzyme feruloyl esterase (EC 3.1.1.73) catalyzes the reaction
Arabinoxylan is a form of the hemicellulose xylan found in both the primary and secondary cell walls of plants which in addition to xylose contains substantial amounts of another pentose sugar, arabinose. The term arabinoxylan usually refers to feruloyl-arabinoxylan from grasses and other commelinids containing moieties of the phenolic ferulic acid that can undergo oxidative coupling forming crosslinks between arabinoxylan chains and with lignin. Whilst arabinose has been found linked to xylan in non-commelinid plants, ferulic acid has not been reported on these and unlike feruloyl-arabinoxylan these arabinoxylans are not monophyletic. The remainder of this article refers to feruloyl-arabinoxylan from cell walls of grasses and other commelinid species.
Phenolic acids or phenolcarboxylic acids are phenolic compounds and types of aromatic acid compounds. Included in that class are substances containing a phenolic ring and an organic carboxylic acid function. Two important naturally occurring types of phenolic acids are hydroxybenzoic acids and hydroxycinnamic acids, which are derived from non-phenolic molecules of benzoic and cinnamic acid, respectively.
8,5′-Diferulic acid is a non cyclic type of diferulic acid. It is the predominant diferulic acid in sugar beet pulp. It is also found in barley, in maize bran and rye. 8,5′-Diferulic acid has also been identified to be covalently linked to carbohydrate moieties of the arabinogalactan-protein fraction of gum arabic.
Triferulic acids, also known as dehydrotriferulic acids, are a type of oligomeric natural phenols formed from ferulic acid.
Decarboxylated 8,5'-diferulic acid is a molecule included in the group but is not a true diferulic acid. It is found in maize bran.
Root mucilage is made of plant-specific polysaccharides or long chains of sugar molecules. This polysaccharide secretion of root exudate forms a gelatinous substance that sticks to the caps of roots. Root mucilage is known to play a role in forming relationships with soil-dwelling life forms. Just how this root mucilage is secreted is debated, but there is growing evidence that mucilage derives from ruptured cells. As roots penetrate through the soil, many of the cells surrounding the caps of roots are continually shed and replaced. These ruptured or lysed cells release their component parts, which include the polysaccharides that form root mucilage. These polysaccharides come from the Golgi apparatus and plant cell wall, which are rich in plant-specific polysaccharides. Unlike animal cells, plant cells have a cell wall that acts as a barrier surrounding the cell providing strength, which supports plants just like a skeleton.